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ORNL-44 15
Contract N0. W-7405-eng-2 6 CHEMICAL TECHNOLOGY DIVISION Chemical Development Section B
LIQUID-VAPOR EQUILIBRIA IN LiF-BeF2 A N D LiF-BeF2-ThF4 SYSTEMS
F. J. Smith L. M. Ferris C. T. Thompson LEGAL NOTICE Thla report was prepared M an account of Qovernment #ponsored work. Neither the United states. nor the Commission, nor any person actlng on behalf of the Commission:
A. Makes any warranty ormpreLlentation. expressed or implied. with respect to the accuracy. completeness. or usefulness of the informanon contained in thls report. or that the use of any Informatlon, apparatus, method, o r procens disclosed in thls report may not infrhge 4 privately owned rlgh* or B. Aasumes any UabWtles with respect to the m of, o r for dnmages resulting from the IW of any information. awnratus. method, or process diaclosed in thls report. 1 As u d Ln the .boss. ''permm actinson hehalf of the CommI~elom"Includsa my emI ployw or contractor of the Commission, o r employee of much contractor, to the extent that such employee or contractor of the Commission, o r employee of much contractor prepares. diswmlnates, o r provides access to, m y Information pursuant to his employment o r contract rtth the Commission. o r his employment with *uch contractor.
JUNE 1969
OAK RIDGE NATIONAL LABORATORY Oak Ridge, Tennessee operated by UNION CARBIDE CORPORATION for the
U. S. ATOMIC ENERGY COMMISSION
... 111
CONTENTS
.............................................. introduction ... ...... .......... .......... . . . . .. . . . . . . Experimental . . .. . . .. .. . . . . . . . . . . .. . . . . . . .. . . .. .. . . . . Results ............................................ 3.1 Systems of Interest in Processing Two-Fluid MSBR Fuel . . . . . . . . . . . 3.2 Systems of Interest in Processing Single-Fluid MSBR Fuels . . . . . . . . . Conclusions . .... .. .. .. .. .. .... .. .. .. .. .. .. . . . . .. . . .. References. .. .. .. . . .. .. .. .. .. .. .. .. .. .. . . .. . . .. . . . .
Page
Abstract
1
1.
1
2.
3.
4. 5.
2 6
6 11
14 15
1
1 LJ
LIQUID-VAPOR EQUILIBRIA IN LiF-BeF, AND LiF-BeF -ThFA SYSTEMS 2L.
I
F. J. Smith, L. M. Ferris, and C. T. Thompson I
ABSTRACT Liquid-vapor equilibrium data for several LiF-BeF2 and LiF-BeF2ThF4 systems were obtained by the transpiration method over the temperature range of 900 to 105OOC. Relative volatilities, effective activity coefficients, and apparent partial pressures are tabulated for the major components, as well as for solutes such as UF4, Z r F 4 CsF, RbF, and some rare-earth fluorides. The values are in reasonable agreement with those reported i n the literature. Results of t h i s study show that distillation may not be feasible as a primary separations method in the processing of single-fluid MSBR fuels.
1. INTRODUCTION
To be an efficient breeder, a molten-salt reactor must be close-coupled to a chemical processing facility to provide for the continuous removal of protactinium, fission products, and corrosion products from the system.
The initial molten-salt
breeder reactor (MSBR) concepts"2 were based on the use of two fluids: a fuel salt composed of LiF-BeF2 (66-34 mole %) containing about 0.3 mole % UF4, and a blanket salt having the approximate composition LiF-BeFq-ThF4
Recently,
3
(73-2-25 mole %).
however, emphasis has been centered on a single-fluid MSBR that would
utilize a salt such as LiF-BeF2-ThF4-UF4
(72-16-12-0.3
mole %). Considerable
4- 7
effort was expended on the development of a fluorination-distil lation method for the processing of the fuel salt from,a two-fluid MSBR.
Fluorination was selected
as the method for removing the uranium from the salt as UF6, and distillation was proposed as the means for separating the rare-earth fission products from the bulk
8
of the LiF-BeFq carrier salt. Results of batch distillation experiments by Kelly
9
and experiments by Scott i n a simple closed vessel w i t h a "cold finger" to collect the vapor sample indicated that the rare-earth separation factors were about 100.
Iti
More recent experiments by Cantor,
10
who used the transpiration method, and by
2 Hightower and McNeese,
11
who used an equilibrium s t i l l , demonstrated that dis-
tillation i s possible and reported rare-earth separation factors of about 1000. Prior to the present study, no experiments were conducted with LiF-BeF -ThF
2
systems;
4 hence, the applicability o f distillation to the processing o f single-fluid MSBR fuels
could not be proper Iy assessed.
This report summarizes the results of experiments i n which the transpiration method of obtaining liquid-vapor equilibrium data was used i n the temperature range of 900 to 105OOC.
These experiments had three obiectives:
(1) to corroborate data
obtained by the equilibrium s t i l l technique w i t h two-fluid MSBR fuel salt, (2) to determine relative volatilities of other components of interest in two-fluid MSBR processing, and
(3) to obtain sufficient data on LiF-BeF2-ThF4 systems to allow a
preliminary evaluation of the applicability of distillation i n the processing o f singlefluid MSBR fuel. Acknowledgments.
-
The authors are indebted to the following members of the
ORNL Analytical Chemistry Division:
the group o f W. R. Laing for the colorimetric
analyses for thorium and uranium; Marion Ferguson for the flame-photometric analyses for lithium and other alkali metals; and C. A. Pritchard for the emission-spectrographic analyses for beryllium, thorium, rare earths, and zirconium. LiF-BeF
2
and LiF-BeF -ThF
Bulk quantities of
of varying compositions were provided by the group o f
2 4 J. H. Shaffer of the ORNL Reactor Chemistry Division.
We thank J. F. Land and
C. E. Schilling for further purifying the small batches of salt used i n the individual experiments.
2. EXPERIMENTAL
I n using the transpiration method w i t h molten salts, an inert (carrier) gas i s passed over a molten salt (becoming saturated w i t h the vapor i n equilibrium with it), through a condenser where the salt vapors are deposited and collected, and, finally, through a Wet Test Meter where the total volume o f inert gas used is determined. After the vapors have transpired for a known period of time a t a given temperature,
3
&.i
the condenser i s removed and the salt contained within i s dissolved. Analyses o f the solution, along with the pressure of the system and the volume of inert gas used, provide the information necessary for calculating apparent partial pressures of the components of the system. The transpiration apparatus, shown schematically i n Fig. 1, closely resembles .. that used by Sense et al.
12
and Cantor. l3The basic Components consisted of a
36-in.-long alumina tube contained i n a 1bin.-long Marshall furnace. A nickel liner was placed inside the alumina tube to protect the alumina from corrosion by the fluoride vapors and to help "flatten" the temperature profile. The temperature profile of the Marsholl furnace was adjusted by the use of shunts until the hottest region of the furnace was located exactly i n the center and the maximum temperature variation (at
1000째C) over
the length of the nickel boat (used to contain the salt sample) was
5OC. The furnace temperature was controlled by a Wheelco "Capacitrol" timeproportional controller and a Chromel- Alumel thermocouple. The temperatures of the melt and vapor were measured by means of Chromel-Alumel thermocouples and a Brown recorder. Salt samples (about 100 g) of the desired composition were initially treated, i n graphite containers, w i t h HF-H2 mixtures at
850 to %O0C
to remove oxide im-
purities; residual HF and H2 were stripped from the salt with high-purity argon. After being cooled to room temperature, each salt ingot was transferred (under argon) to the nickel boat, which was placed i n the center
of the Marshall furnace. The
transpiration apparatus was heated ( w i t h argon flowing slowly) to the desired temperature. Then a condenser was inserted into the system, and transpired vapors were collected over a predetermined length of time. Each condenser (made of 1/4-in.-diam
nickel tubing) had a 1/32-in.-diam
hole
i n the end that was i n contact w i t h the vapor phase above the salt sample. The carrier gas was high-purity argon that had been further purified by passage through a Moleculor Sieve trap to remove water and through a heated (45OOC) trap filled
w i t h metallic copper to remove oxygen. Removal and replacement of the condensers
W
could be accomplished while the system remained a t temperature; thus duplicate
ORNL-DWG 68-9t8t
HIGH-TEMPERATURE ALUMINA TUBE (36 in. LONG)
NICKEL
THERMOCOUPLE FOR VAPOR TEMPERATURE 1 ARGON INLET -'T
L
m
I
I
I
ARGON TO WET TEST METER
I
lCONDENSER
Fig. 1. Cross Section of Transpiration Apparatus Used to Determine Relative Volatilities i n Molten Salt Systems.
c
P
5
b i .
samples at a given temperature and/or a series of samples at different temperatures could be obtained using a single batch of salt.
After a condenser was removed, i t s
The condenser was then
exterior was polished to remove surface Contamination.
cut into sections, and the salt contained within was recovered by leaching the
-
sections with 1 N H2S04. analyses.
Aliquots of the leachate were submitted for the desired
.
Apparent partial pressures were calculated from the following expression:
PA =
H
NA + NB+
..... Nn + M
'
where = the apparent partial pressure of species A,
P = the total pressure of the vaporized salt and carrier gas,
NA = total moles of species A collected i n the condenser, and M = total moles of carrier gas passed through the system.
This expression was derived by assuming that the behavior of each gas was ideal and that Dalton's law o f partial pressures was applicable. The transpiration method gives no direct information about the molecular formulas of the vapor species
or about the total vapor pressure o f the system. Therefore,
i t was assumed that each species existed as the monomer i n the vapor phase.
using this method, the gas flow rate must be carefully controlled. (i.e.,
In
If i t i s too high
greater than the rate at which evaporation occurs at the liquid surface), the
carrier gas w i l l not become saturated w i t h vapor and the measured value of the vapor pressure w i l l be low.
If it i s too low, thermal diffusion effecfs in the vapor
phase w i l l make the calculated value of
PA too large.
For the experimental ap-
paratus described above, the measured vapor pressure o f a typical salt was found to be independent o f the argon flow rate i n the range of 15 to 50 cc (STP)/min. fore, no correction was needed for diffusion or kinetic effects.
There-
Under the conditions
used, no change i n the composition of the liquid phase was detected during the course
LJ
of an experiment.
6 3. RESULTS
3.1
Systems of Interest i n Processing Two-Fluid MSBR Fuel
Data obtained for LiF-BeF and LiF-BeF2-metal fluoride systems are given in
2
Table 1.
I n the absence o f any information regarding complex molecules i n the
vapor phase, the partial pressures of LiF, BeF
2'
and solute fluorides were calculated Y
by assuming that only monomers existed in the vapor. apparent partial pressures, P
A
In each experiment, the
,could be described adequately by the linear expression
log PA (mm of Hg) = a
- b/T(OK)
,
i n which a and b were constants over the temperature range investigated, 900 to
105OOC.
Typical plots of log P vs
1/T
are shown i n Figs. 2 and
3.
Other workers have expressed their vapor-liquid equilibrium data i n terms of relative volatility, which i s defined by:
where
a
AB
i s the relative volatility of component A
w i t h respect to component B,
y i s the mole fraction of the designated component i n the vapor phase, and x i s the mole fraction in the liquid phase.
the relative volatilities of BeFp (with respect to
LiF) obtained i n our experiments w i t h LiF-BeF binary systems are i n reasonable agreement with those reported by Cantor, For example, Cantor obtained values of and
3.75 for
LiF-BeF2
study were about
(90-10mole %);
lo, la who also used the transpiration method.
4.28 for
LiF-BeF2
the corresponding values from the present
3.8 and 3.77 (Table 1).
Our value obtained w i t h LiF-BeF2 (90- 10
mole %) i s somewhat lower than the average value of and McNeese,
11
(85-15mole %) at 1000째C
4.71
reported by Hightower
who used an equilibrium s t i l l method, and i s higher than our values
obtained when the salt contained small amounts of RbF, CsF, "F4
(Table 1). This
scatter i n values i s not surprising, however, because small variations i n the composition of the liquid and/or vapor cause large changes i n the relative volatility value. For
7
Table 1. Apparent Pcrtial Pressures, Relative Volatilities, and Effective Activity Coefficients i n LiF-BeF2--Metal Fluaide Systems Apparent Pcrtial Pressue,* lag P (mm) =
Salt Composition (mole %)
LiF
BeF2
86
14
90
95
Third Component
10
a Species
89.6
86.4
90
89.9
90
10
9.9
9.6
10
IO
10
UF4: 0.02
UF4: 0.5
UF4: 4.0
Rbk 0.09
CsF: 0.03
ZrFq: 0.083
b
8.497
11,055
bF2
7.983
10,665
LiF
7.604
10,070
BeF2
8.707
11,884
8.804
11,505
11.510
15,303
LiF
9.48 1
12,386
BeF2
9.339
12,4 1 1
BeF2 90
a
(OK)
LiF
LiF
5
- b/T
Effective Activity Coefficient at
looooc
Relative Volatility, with Respect to LiF, at 10000c
1.60 4.42~
3.82
1.30 3.55x 10-2
3.77
1.30 4.33x 10-2
4.60
1.33 5 . 9 6 ~IOm2
uF4
4.361
12,481
7 . 3 6 ~10-3
LiF
8.384
10,987
BeF2
7.42 1
IO, 112
4.65~
UF4
6.686
13,443
1.09 x
LiF
10.790
13,992
BeF2
IO. 177
13,726
3.84~
UF4
10.272
16,786
1.25 x
LiF
8.286
10,8l 1
6.19 2 . 9 ~lom2
1.34 4.78 4.2 x
1.55 3.42 4.2~
1.47 3.1 1 x
BeF2 RbF
6.596
10,552
5.187
8,907
2.19
LiF
9.654
13,459
1.99
2.93 24.7
BeF2
8.310
11,313
4 . 0 7 ~ lom2
GF
0.819
3,375
1.17
LiF
7.915
10,358
BeF2
7.167
10,070
2.83~
2.77
zrF4
13.095
20,382
3 . 0 5 ~10-4
2. I 9
2.82 95.1
1.41
*Temperature range: 900 to 1C50째C. It was assumed that UF, BeF2, and the solute fluaides existed only as monomers in the wpor.
8
u ORNL-DWG
10'
68-9482
IO0 n
CT
I E
E
Y
w
a
lo-'
3 v)
v)
W
a a -l lcr2 a -
I-
C
a a I-
=
w
10-~
a
2a
a
ZrF4 I RbF 7.6
7.8
8.0
6.2
8.4
8.6
lo~ooo/T(OK) Fig. 2. Apparent Partial Pressure-Temperature Curves for the Systems LiF-BeF2-RbF (90- 10.0-0.09 mole %) and LiF-BeF2-ZrFq (90- 10.0-0.083 mole %).
*
i
9
I*I ORNL-DWG 68-9483
II
TEMPERATURE ("C)
1
'0'
'050
1000
900
950
LiF A
ioo
BeF2 UF4
CI
0
I
E
L io4 W
cr 3 cn cn W
cr a a -I 40-2
i
F
U
i 9
s W
g io-3 a
a
rG4
rG5 7.6
7.8
8.0
'
8.2
8.4
8.6
(OK )
Fig. 3. Apparent Partial Pressure-Temperature Curves for the System LiF-BeF2-UF4 (86.4-9.6-4.0 mole %).
.
example, i t has been reported
11
that LiF-BeF2 (66-34 mole %) i s the vapor i n
equilibrium with LiF-BeF2 (90-10 mole %) at 1000째C.
This gives a value for the
relative volatility of BeF2:
OL=
Another source
13
.
&10/90=4.64
has reported that the composition of the vapor i n equilibrium w i t h
LiF-BeF2 (88- 12 mole %) i s LiF-BeF2 (67-33 mole %), corresponding to
.
33/67
&=~12j/88= 3.6
Our partial pressure data for LiF-BeF system are incompatible with some of the total pressure data presented by Cantor.
13
He has reported the total pressure
of LiF-BeF2 (90-10 mole %) to be 1.8 mm Hg at 1000째C.
10oO째C, we obtained the approximate values PLiF
- 0.55
For the same system at and PBeF2 = 0.23 mm Hg,
corresponding to a total pressure of 0.78 mm Hg (assuming that no dissociation or association occurred i n the vapor phase). The total pressure calculated from our transpiration data should have been higher than the actual total pressure because association in the vapor phase undoubtedly occurs. pure LiF has been noted,
Association in the vapors above
15
and complexation has been observed (by mass spectro16 metry) i n the vapors above LiF-BeF solutions.
2
Effective activity coefficients, yA, were calculated for each component of the LiF-BeF2 systems (Table 1).
The activity coefficient for component A i s given by:
YA =
'A
1 '
i s the mole fraction of A in the solution, P i s the apparent partial presA A 0 sure of A, and PA i s the vapor pressure of pure A. The activity coefficients obtained 8 for BeF2 are i n good agreement w i t h those reported by Kelly, who used distillation 11 data and assumed the activity for LiF to be unity. Hightower and McNeese noted where
X
that the relative volatilities obtained experimentally for several rare earths were
ci
j
j
11
I
LJ
very close to those calculated by assuming ideal solution behavior (Raoult's law;
y = 1).
The results of the study presented in this report show that RbF and CsF also
behave almost ideally; their activity coefficients are near unity (Table 1). Uranium tetrafluoride and 2F4, on the other hand, do not behave ideally i n solution; activity
-2
to 10
coefficients for these solutes were only
(Table 1). The vapor pressures,
at 10oO째C, of the pure fluorides of interest are given i n the following table:
Component
Vapor Pressure at 1oOOo C (mm Hg)
L iF
0.47
Reference
17
BeF2
65.
18
ZrF4
4770
19
UF4 RbF CsF
2.44
20
7.8
17
76
ThF4
17 21
0.0668
3.2 Systems of Interest in Processing Single-Fluid MSBR Fuels Liquid-vapor equilibrium studies o f several LiF-BeF2-ThF4 systems have been made to determine the feasibility of using certain distillation steps in the processing of single-fluid MSBR fuels.
The data are summarized in Table 2.
pressure--temperature plot i s shown in Fig. 4.
A typical partial-
The partial pressures and the predicted
total pressures were calculated assuming that only monomen existed i n the vapor. Corrections for association in the vapor (known to occur i n the vapor above pure LiF and LiF-BeF2 systems) would cause both the calculated partial pressures and the predicted total pressures to be lower.
In addition to the systems shown in Table 2, a limited amount of data was obtained with LiF-BeF -ThF -solute fluoride systems.
2
4
LiF-BeF2-ThF4-LaFg (36.6- 1.0-59.6-2.8
Results obtained for the system
mole %) gave the following relative
12
Table 2 Apparent . Jitial Presswes, RelativeVolatilities, and Effective Activity -.efficienh i n LiF-
~~~~~~~
Salt Composition
(mole %) LF BeF2 68
70.5
75.4
53.5
45
34
20
7.5
3.6
1.5
0.06
1.0
ThF4 12
22
21
45
55
65
~
Vapor Composition at looO째C (mole%) LiF BeF2 ThF4 29
36.7
43.2
165
75.1
9.9
71
63.1
55.6
81.5
12
85.2
0.07
0.2
1.1
2.1
12.7
4.8
&we* log p(mm) = A
- Bh
Partial Pressurea
Species
-ThF4 System
~
~
A
B
Effectiw Activity Coefficient at 1000째C
Relative Volatility at 1000째C
2.44
-
LiF
7.806
10,070
BeF2 ThF4
9.194
11,349
C
C
LiF
8.510
11,352
1.19
BeF2
7.801
10,112
0.14
16.2
ThF4
4.360
8,935
0.15
0.018
LiF
8.548
10,112
0.98
27.1
0.146 -0.25
BeF2
7.480
9,984
0.19
ThF4
2.879
6,233
0.6 1
LiF
8.446
12,285
BeF2 ThF4
d
d
10.575
16,146
0.27
LiF
8.61 1
11,826
0.23
d
d
-0.20
-
1.1
0.81
-
0.38
-I77
0.15 0.06
-120
10.314
16,459
0.23
0.14
LiF
10.314
12, 129
0.13
-
BeF2 ThF4
d
d
11.539
17,232
0.24
2.7
0.088
BeF2 ThF4
-0.28
(mm Hg)
8.27 -0.014
0.25 -0.32
Predicted Total Pressure at IOOOOC
0.21
-293 0.26
'Teenperatwe range: 950 to 105OOC It was assumed that no associationoccurred i n the vapor. bCalculated on the assumption that no association occurred in the vapor. Association, which undoubtedly occur, would make the actual total pressure less than the volue predicted here. 'The rcatta i n data points was too great for determination of these values. dlhe BeF2 concentration i n the liquid phase decreasedtoo rapidly to allow determination of these values.
13 ORNL- DWG 68- 9484
1050
TEMPERATURE ("C) 1000 950
IO'
IO0 h
P,
I
E
E
U
W
5 40" v) v)
W
U
a J
a
F U
i 3 Id2 t-
z W U
8 a
a
{o-~
IO-^ 7.6
7.0
8.0 409000/7.
(0
8.2
8.4
K)
Fig. 4. Apparent Partial Pressure-Temperature Curves for the System LiF-BeF2-ThF4 (70.5-7.5-22 mole %).
14 volatilities (with respect to LiF) at loOO°C: BeF2, 37; ThF4, 0.25; and LaF3,
1.5 x
Data for the system LiF-BeF2-ThF4-CsF-RbF
(33.0-0.66-63.1-1.36-
1.98 mole %) yielded relative volatilities of about 100,0.65,3.7, and 1.0 for BeF2, ThF4, CsF, and RbF, respectively, at 1000°C.
The total pressure predicted
for this system at 1000°C is less than 0.05 mrn Hg. In contrast to the observation made with LiF-BeF2 systems, the behavior of GF and RbF was far from ideal. The -3 effective activity coefficients for these two solutes were 3 x 10 and 8 x respectively.
This marked departure from ideality is probably due to complexation
of the alkali-metal fluorides with ThF4. (Note that the ThF4/LiF mole ratio in this salt was rather high.)
In another experiment at 10oO°C with LiF-BeF2-ThF4-
CsF-RbF (68-20-12-0.13-0.08 mole %), a salt having a much lower ThF4/LiF mole ratio, both GF and RbF behaved much more ideally; the effective activity coefficients were 1.6 and 17, respectively.
The corresponding relative volatilities
(with respect to LiF) were 107 and 119. Data from a run with LiF-BeFg-ThF4-EuFg (42.4-0.06-51.8-5.8
mole %) yielded a relative volatility of about 9 x
for
EuF3 at 1000°C. 4. CONCLUSIONS
Measurements made with three different LiF-BeF2 solutions indicated that a melt having the approximate composition LiF-BeF2 (90-10 mole %) will, at 1000°C, be in equilibrium with vapor having the composition LiF-BeF2 (66-34mole %). The
latter composition is that desired for the fuel salt for a iwo-fluid MSBR. The results of this study show that recovery of the UF4 and most of the LiF and BeF2 from the fuel salt of a two-fluid MSBR, leaving fission products such as the rare earths in the still-pot bottoms, is not possible in a single-stage distillation system because the volatility of the W4 is too low. The fluorides of the fission products cesium, zirconium, and rubidium have high relative volatilities, and would therefore concentrate in the distillate with the LiF and BeF2.
Although the relotive volatilities
of the various components are different, a complicated multistage distillation system would be required to effect the desired separations. Thus, these results support the
15 original conclusion4 that distillation i s best applied to the processing of two-fluid
MSBR fuel salt after the uranium has been removed by fluorination. The few results obtained with LiF-BeF2-ThF4 systems showed that the volatilities of both the rare-earth fluorides and ThF are low, even at 1000째C.
It i s possible 4 that the rare-earth-thorium separation required in the processing of single-fluid MSBR
fuels could be achieved by distillation; however, the results of this work indicate that the temperature required to achieve adequate distillation rates would have to be at least 12OOOC. Thus, determination
of relative volatilities for the rare-earth
fluorides and ThF4 at temperatures above 1000째C w i l l be required in order to assess
the feasibility of utilizing distillation in the processing of single-fluid MSBR fuels.
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17
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